Method of performing an ion exchange of optical glass

ABSTRACT

This invention relates to a method of performing an ion exchange of optical glass to produce an axial gradient index material having a good linear distributiion by bringing a glass body containing a monovalent cation component into contact with a medium containing a monovalent cation component and exchanging these cation components under a predetermined condition.

This is a continuation-in-part of application Ser. No. 507,881, filed Apr. 12, 1990, abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of manufacturing optical glass having a gradient index and, more particularly, a method of manufacturing optical glass having a gradient index in a direction of the optical axis.

2. Prior Art

Optical glass is generally required to have a uniform refractive index. Optical glass and lens materials having gradient indices having controlled profiles have been developed and commercially available in recent years.

Gradient index lenses are classified into the following three types of lens:

Radial gradient index lens;

Axial gradient index lens; and

Spherical gradient index lens.

An example of the axial gradient index lens is shown in FIG. 19. A lens 1 has a gradient index monotonously decreased from a vertex 1A of its convex spherical surface to almost perfectly correct spherical aberration occurring on the convex spherical surface. A function for the axial gradient index can greatly enhance the aberrational correction by defining a refractive index n(z) at a distance z, as shown in FIG. 19, as follows:

    n(z)=n0-kz                                                 (1)

where n0 is the refractive index at the vertex 1A of the convex surface, z is the length in the direction of thickness along the optical axis when the vertex of the convex surface is defined as an origin, and k is a positive constant. The distribution defined by equation (1) is called a linear distribution hereinafter. In order to obtain a lens having excellent optical characteristics, axial gradient index glass having a linear distribution or a distribution close to a linear distribution is prepared, and the glass is formed into a lens. When a refractive index difference Δn shown in FIG. 19 is increased, freedom in lens design is increased to facilitate aberrational correction. Therefore, a larger refractive index difference Δn is preferred.

An ion exchange method is generally employed as a method of manufacturing axial gradient index glass. More specifically, a flat glass body containing a monovalent ion component is dipped in a molten salt such as KNO₃, NaNO₃ or TlNO₃ to form a concentration distribution of Li+, Na+, K+ or Tl+ ions in the glass body, thereby obtaining a gradient index corresponding to the concentration distribution.

Since, however, a monovalent ion exchange is a diffusion phenomenon, a gradient index obtained by the ion exchange method is not linear as shown in FIG. 19, but has one of the following distribution curves as shown in FIG. 20:

Distribution curve having an upward convex shape;

Distribution curve having a downward convex shape; and

S-shaped distribution curve.

Even if a glass material having such a gradient index is formed into a lens, it is difficult to correct the aberration.

OBJECT AND SUMMARY OF THE INVENTION

It is an object of the present invention to solve the conventional drawbacks described above and to provide a method of performing an ion exchange of optical glass to produce an axial gradient index material having a good linear distribution.

According to the extensive studies of the present inventors, when a composition of a monovalent cation component contained in a glass body and a composition of a monovalent cation component contained in a medium satisfied a predetermined condition, it was found that an axial gradient index having almost a linear index distribution could be obtained by the ion exchange method.

The monovalent ion component contained in the glass body serves to increase a refractive index. Of all the monovalent ion components, Tl₂ O has a maximum effect for increasing the refractive index. In order to obtain a large refractive index difference, it is most suitable to form a concentration distribution of Tl₂ O.

In order to form a concentration distribution of Tl₂ O by the ion exchange method,

the Tlhd 2O concentration in the glass body is set to be higher than the Tl+ concentration in the medium to decrease the Tl₂ O concentration on the glass surface, or

the Tl₂ O concentration in the glass body is set to be lower than the Tl+ concentration in the medium to increase the Tl₂ O concentration on the glass surface.

Glass containing a large amount of Tl₂ O is unstable, and the latter method is therefore suitable.

Conditions to be satisfied by the glass and the medium prior to the ion exchange process will be described below.

As a total sum M₂ O(=Tl₂ O+K₂ O+Na₂ O+Li₂ O of the monovalent cation concentration in the glass body is increased, a larger refractive index difference can be obtained, thus deriving the following condition:

    8 mol % ≦M.sub.2 O (=Tl.sub.2 O+K.sub.2 O +Na.sub.2 O+Li.sub.2 O)≦30 mol %                                        (2)

If the total sum M₂ O is smaller than 8 mol %, a sufficiently large refractive index difference cannot be obtained. However, if the total sum M₂ O exceeds 30 mol %, chemical resistance of glass is degraded.

When a Tl₂ O component is contained in a glass body, a refractive index difference obtained by the ion exchange process is disadvantageously decreased. According to the extensive studies of the present inventors, when a Tl₂ O component was contained in a glass body in a predetermined amount, it was effective to contain Tl₂ O in the glass body in the following range to improve linearity of the gradient index:

    0 ≦(Tl.sub.2 O≦12 mol %                      (3)

When the content of Tl₂ O is increased, the refractive index difference is decreased and at the same time an amount of relatively expensive Tl₂ O to be used is increased. Therefore, the content Tl₂ O preferably falls within the range of 0.9 mol % or less.

Other major monovalent cation components except for Tl₂ O are Na₂ O, K₂ O and Li₂ O. Of these components, when the content of K₂ O is increased, a glass transition point Tg of the glass body is increased. In this case, the temperature of the ion exchange process can also be increased, and the ion exchange process time can be advantageously shortened.

Glass forming components in addition to the monovalent ion component are silicates, borates and phosphates.

As a medium of the ion exchange, molten salts, e.g., nitrates, sulfates or chlorides can be used. Of these components, a nitrate (e.g., a mixed salt of TlNO₃, NaNO₃ and KNO₃) which can minimize glass erosion is suitable. When the content of TlNO₃ in the mixed salt is increased, a refractive index difference can be increased. When the content of TlNO₃ is excessively increased, linearity of the gradient index is degraded, and at the same time a decomposition reaction of TlNO₃ is excessively accelerated. Therefore, the TlNO₃ concentration falls within the following condition:

    1≦TlNO.sub.3≦ 10 mol %                       (5)

The above problem typically occurs when the content of TlNO₃ exceeds 10 mol %.

In order to suppress the decomposition reaction of the nitrate and minimize glass erosion, the content of KNO₃ must be increased to satisfy the following condition:

    78≦KNO.sub.3≦ 99 mol %                       (6)

In addition, when NaNO₃ is added to a salt mixture of KNO₃ and TlNO₃ within the following range:

    0≦NaNO.sub.3≦ 12 mol %                       (7)

linearity of the gradient index can often be improved.

The gradient index of the glass upon the ion exchange process under the above-mentioned conditions is almost linear in the direction of depth from the surface.

The range of M₂ O content is 8 mol % ≦M₂ O ≦30 mol % (M₂ O represents an oxide of a monovalent element).

M₂ O includes Tl₂ O as previously stated.

N_(Tl) represents the ratio of Tl₂ O content to the whole of the M₂ O content.

N_(Tl) is defined by equation (3) as O≦NT₁ ≦0.4.

Thus, 30 mol % which is the maximum of Tl₂ O content ×0.4 which is the maximum value of N_(Tl) equals 12 mol %.

Similarly if NT₁ equals 0.3 30 mol % ×0.3=9 mol %.

M₂ O comprises Tl₂ O, K₂ O, Na₂ O and Li₂ O.

The total sum of M₂ O equals Tl₂ O+K₂ O+Na₂ O+Li₂ O.

Tl₂ O ≦12 mol %.

1≦TlHO₃ ≦10 mol %.

78 mol % ≦KNO₃ ≦99 mol %.

O ≦NaNO₃ ≦12 mol % and,

1≦TlNO₃≦ 10 mol %.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 16 are graphs showing gradient indices of Examples 1 to 16 according to the present invention, in which a light wavelength is set to be 587.6 nm;

FIGS. 17 and 18 are graphs showing gradient indices of Comparative Examples 1 and 2 except for the present invention, in which a light wavelength is set to be 587.6 nm;

FIG. 19 is a view showing an axial gradient index lens;

FIG. 20 is a graph showing a gradient index which is not suitable for an axial gradient index lens;

FIG. 21 is a view for explaining an ion exchange processing apparatus; and

FIG. 22 is a graph for explaining n_(d) and Δn in Table 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention will be described in detail below with reference to an embodiment shown in the accompanying drawings.

As shown in FIG. 21, a nitrate was placed in a stainless steel vessel 3 having a lid and a volume of about 1,000 ml and was heated in an electric furnace to obtain a molten salt 4. Preheated flat glass (50×60 ×3 mm) 5 was dipped in the molten salt 4 to perform an ion exchange process at a predetermined temperature. The flat glass 5 was kept upright by a stainless steel holder. Upon completion of the ion exchange, the flat glass 5 was taken out from the molten salt 4, gradually cooled, and washed with water. The gradient index of the flat glass 5 was measured as follows:

The flat glass was cut into about 20 pieces each having a size of 5×5 mm;

The surfaces (one major surface) of the pieces were cut by different depths (e.g., 0 μm, 20 μm, 40 μm, . . . ); and

The cut surfaces were polished, and their refractive indices (λ=587.6 nm) were measured by a refractometer.

EXAMPLES

Compositions of flat glass samples and their N_(Tl) values prior to the ion exchange process are shown for Examples 1 to 16 in Table 1. The compositions of molten salts, ion exchange temperatures, ion exchange times, refractive indices n_(d) of glass samples prior to the ion exchange process and refractive index differences Δn after the ion exchange process are summarized in Table 2 (FIG. 22).

The gradient indices of the samples after the ion exchange process are almost linear, as shown in FIGS. 1 to 16. The samples can be used as materials for axial gradient index lenses.

COMPARATIVE EXAMPLES

Compositions of flat glass samples and ion exchange conditions are summarized for Comparative Examples 1 and 2 in Tables 1 and 2. The content of TlNO₃ of Comparative Examples 1 and 2 are 12 mol % each, and do not satisfy the following condition of the present invention:

    1≦TlNO.sub.3≦ 10 mol %

The gradient indices of Comparative Examples 1 and 2 are shown in FIGS. 17 and 18, respectively. Since the gradient index is greatly deviated from a straight line, these samples of Comparative Examples 1 and 2 are not suitable as materials for axial gradient index lenses.

                                      TABLE 1                                      __________________________________________________________________________     Unit: mol %                                                                                                        Other                                                                               Other                                                          Tl.sub.2 O Compo-                                                                              Compo-                                Component                                                                            SiO.sub.2                                                                         B.sub.2 O.sub.3                                                                   MgO                                                                               CaO                                                                               ZnO                                                                               ZrO.sub.2                                                                          (N.sub.T1)                                                                         Na.sub.2 O                                                                         K.sub.2 O                                                                         nents                                                                               nents                                 __________________________________________________________________________     Example 1                                                                            55.0                                                                              5.0                                                                               -- -- 20.0                                                                              --  4.0 11.0                                                                               5.0                                                                               --   --                                                             (0.20)                                                Example 2                                                                            55.0                                                                              3.5                                                                               4.0                                                                               --  8.0                                                                              1.0 4.0 14.0                                                                               4.0                                                                               Li.sub.2 O                                                                          TiO.sub.2                                                      (0.16)     3.5  3.0                                   Example 3                                                                            53.0                                                                              3.5                                                                               4.0                                                                               4.0                                                                                9.0                                                                              1.0 4.0 14.0                                                                               4.0                                                                               Li.sub.2 O                                                                          --                                                             (0.16)     3.5                                        Example 4                                                                            50.0                                                                              -- 2.0                                                                               3.0                                                                               15.0                                                                              --  4.0 10.0                                                                               6.0                                                                               GeO.sub.2                                                                           --                                                             (0.20)     10.0                                       Example 5                                                                            57.0                                                                              -- 5.0                                                                               5.0                                                                               10.0                                                                              --  3.0  8.0                                                                               9.0                                                                               Al.sub.2 O.sub.3                                                                    --                                                             (0.15)     3.0                                        Example 6                                                                            50.0                                                                              5.0                                                                               5.0                                                                               -- 15.0                                                                              1.0 3.0  6.0                                                                               6.0                                                                               Li.sub.2 O                                                                          Sb.sub.2 O.sub.3                                               (0.14)     7.0  2.0                                   Example 7                                                                            60.0                                                                              5.0                                                                               -- -- 15.0                                                                              --  2.0 --  18.0                                                                              --   --                                                             (0.10)                                                Example 8                                                                            53.0                                                                              5.0                                                                               10.0                                                                              10.0                                                                              -- 2.0 2.0 14.0                                                                               4.0                                                                               --   --                                                             (0.10)                                                Example 9                                                                            67.0                                                                              5.0                                                                               3.0                                                                               -- 15.0                                                                              --  1.5  2.5                                                                               6.0                                                                               --   --                                                             (0.15)                                                Example 10                                                                           55.0                                                                              5.0                                                                               5.0                                                                               -- 15.0                                                                              --  --  14.0                                                                               6.0                                                                               --   --                                    Example 11                                                                           53.0                                                                              5.0                                                                               10.0                                                                              -- 10.0                                                                              1.0 --  10.0                                                                               10.0                                                                              Sb.sub.2 O.sub.3                                                                    --                                                                        1.0                                        Example 12                                                                           60.0                                                                              5.0                                                                               -- -- 15.0                                                                              --  5.0 --  15.0                                                                              --   --                                                             (0.25)                                                Example 13                                                                           61.0                                                                              -- 3.0                                                                               -- 10.0                                                                              1.0 4.0  8.0                                                                               10.0                                                                              PbO  --                                                             (0.18)     3.0                                        Example 14                                                                           61.0                                                                              -- 3.0                                                                               -- 10.0                                                                              1.0 4.0  8.0                                                                               10.0                                                                              BaO  --                                                             (0.18)     3.0                                        Example 15                                                                           50.0                                                                              5.0                                                                               5.0                                                                               8.0                                                                                7.0                                                                              1.0 3.0  6.0                                                                               8.0                                                                               Li.sub.2 O                                                                          --                                                             (0.13)     7.0                                        Example 16                                                                           55.0                                                                              5.0                                                                               -- -- 20.0                                                                              --  4.0 11.0                                                                               5.0                                                                               --   --                                                             (0.20)                                                Compara-                                                                             61.0                                                                              -- 3.0                                                                               -- 10.0                                                                              1.0 4.0  8.0                                                                               10.0                                                                              PbO  --                                    tive Ex-                 (0.18)     3.0                                        ample 1                                                                        Compara-                                                                             55.0                                                                              5.0                                                                               5.0                                                                               -- 15.0                                                                              --  --  14.0                                                                               6.0                                                                               --   --                                    tive Ex-                                                                       ample 2                                                                        __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     Molten Salt       Ion Exchange                                                                          Ion Ex-                                               Composition (mol %)                                                                              Temperature                                                                           change       Gradient                                 KNO.sub.3 NaNO.sub.3                                                                         TlNO.sub.3                                                                         (°C.)                                                                          Time (hr)                                                                            n.sub.d                                                                            Δn                                                                          Index                                    __________________________________________________________________________     Example 1                                                                            92.5                                                                               --  7.5 485    792   1.6045                                                                             0.044                                                                             FIG. 1                                   Example 2                                                                            93.5                                                                               --  6.5 470    840   1.5970                                                                             0.056                                                                             FIG. 2                                   Example 3                                                                            96.0                                                                               --  4.0 480    840   1.5927                                                                             0.046                                                                             FIG. 3                                   Example 4                                                                            82.0                                                                               10.0                                                                               8.0 470    648   1.6198                                                                             0.049                                                                             FIG. 4                                   Example 5                                                                            93.5                                                                               --  6.5 470    840   1.5759                                                                             0.055                                                                             FIG. 5                                   Example 6                                                                            96.0                                                                               --  4.0 480    840   1.6039                                                                             0.039                                                                             FIG. 6                                   Example 7                                                                            96.0                                                                               --  4.0 480    840   1.5489                                                                             0.048                                                                             FIG. 7                                   Example 8                                                                            93.5                                                                               --  6.5 470    840   1.5597                                                                             0.070                                                                             FIG. 8                                   Example 9                                                                            90.5                                                                               --  9.5 475    792   1.5394                                                                             0.016                                                                             FIG. 9                                   Example 10                                                                           96.0                                                                               --  4.0 480    840   1.5243                                                                             0.050                                                                             FIG. 10                                  Example 11                                                                           96.0                                                                               --  4.0 480    840   1.5349                                                                             0.060                                                                             FIG. 11                                  Example 12                                                                           96.0                                                                               --  4.0 480    840   1.5763                                                                             0.021                                                                             FIG. 12                                  Example 13                                                                           93.5                                                                               --  6.5 470    840   1.6036                                                                             0.037                                                                             FIG. 13                                  Example 14                                                                           82.0                                                                               10.0                                                                               8.0 470    648   1.5951                                                                             0.070                                                                             FIG. 14                                  Example 15                                                                           96.0                                                                               --  4.0 480    840   1.5819                                                                             0.014                                                                             FIG. 15                                  Example 16                                                                           90.5                                                                               --  9.5 485    480   1.6045                                                                             0.065                                                                             FIG. 16                                  Compara-                                                                             88.0                                                                               --  12.0                                                                               475    792   1.6036                                                                             0.076                                                                             FIG. 17                                  tive Ex-                                                                       ample 1                                                                        Compara-                                                                             88.0                                                                               --  12.0                                                                               475    792   1.5243                                                                             0.091                                                                             FIG. 18                                  tive Ex-                                                                       ample 2                                                                        __________________________________________________________________________

According to the present invention, an axial gradient index material having a good linear distribution can be manufactured by the ion exchange process. Therefore, the present invention greatly contributes to the manufacture of axial gradient index lenses having excellent optical characteristics.

Having described a specific preferred embodiment of the present invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to that precise embodiment, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined in the appended claims. 

What is claimed is:
 1. A method for producing axial gradient index materials having an approximate linear distribution, comprising the step of: immersing a glass body having a lens shape, said glass consisting of monovalent ion components, in an ion exchange medium with said medium consisting of ion components to exchange ions, wherein said glass body is optical glass, wherein the composition of said glass body consists of the following components by their approximate molar percentages;

    ______________________________________                                                 SiO.sub.2                                                                            50-67                                                                    Tl.sub.2 O                                                                           0˜12                                                               K.sub.2 O                                                                            4˜18                                                               Na.sub.2 O                                                                           0˜14                                                               Li.sub.2 O                                                                           0˜7                                                                |rO.sub.2                                                                   0˜2                                                                B.sub.2 O.sub.3                                                                      0˜5                                                                MgO   0˜10                                                               CaO   0˜10                                                               ZnO   0˜20                                                               GeO.sub.2                                                                            0˜10                                                               TiO.sub.2                                                                            0˜3                                                                Al.sub.2 O.sub.3                                                                     0˜3                                                                Sb.sub.2 O.sub.3                                                                     0˜2                                                                BaO   0˜3                                                                PbO   0˜3                                                        ______________________________________                                    

wherein the total sum M₂ O of the monovalent ion concentration in said glass body prior to the ion exchange is in the range of 8˜30 molar % and wherein M₂ O is equal to the sum of Tl₂ O, K₂ O, Na₂ O, Li₂ O, and wherein the sum of the components B₂ O₃, MgO, CaO, ZnO, ZrO₂ BaO, and PbO in said glass is in the range of 16.5 to 27 mol %, wherein said ion exchange medium is a molten salt solution consisting essentially of T1NO₃, KNO₃, and NaNo₃, in the molar percentages, 1˜10, 78˜99, and 0˜12, respectively. 